CN114597492A - Nonaqueous electrolyte solution and lithium ion battery using same - Google Patents

Nonaqueous electrolyte solution and lithium ion battery using same Download PDF

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CN114597492A
CN114597492A CN202110389002.4A CN202110389002A CN114597492A CN 114597492 A CN114597492 A CN 114597492A CN 202110389002 A CN202110389002 A CN 202110389002A CN 114597492 A CN114597492 A CN 114597492A
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lithium
carbonate
formula
silicon
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岳敏
曾益平
刘杰
李斌
王献明
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Shenzhen Yanyi New Materials Co Ltd
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Shenzhen Yanyi New Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a nonaqueous electrolyte solution and a lithium ion battery using the same. The invention provides an aryl sulfate-containing nonaqueous electrolyte, which comprises a lithium salt, an organic solvent and an additive, wherein the additive comprises aryl sulfate and a silicon-containing compound, and can further comprise fluoroethylene carbonate, and can also further comprise other additives such as 1, 3-propane sultone, vinylene carbonate, triallyl isocyanurate and the like. The non-aqueous electrolyte can improve the high-temperature storage performance of the lithium ion battery, and simultaneously obviously improve the low-temperature cycle performance, the discharge performance and the safety performance of the lithium ion battery.

Description

Nonaqueous electrolyte solution and lithium ion battery using same
Technical Field
The present invention relates to a nonaqueous electrolyte solution and a lithium ion battery using the same.
Background
The lithium ion battery has the advantages of high voltage, large specific energy, long cycle life, good safety performance, small self-discharge, quick charge, wide working temperature range and the like, and is widely applied to the fields of electronic products, electric tools, energy storage equipment, new energy vehicles and the like. With the expansion of the application scenes of lithium ion batteries, people begin to pay attention to the performances of the lithium ion batteries, such as high and low temperature performance, overcharge performance, high-rate charge and discharge performance and the like under extreme conditions.
The nonaqueous electrolyte is an important component of the lithium ion battery, and has great influence on the high-temperature performance, the low-temperature performance and the cycle performance of the battery. However, in general, from the perspective of the non-aqueous electrolyte, it is difficult to improve both the high-temperature performance and the low-temperature performance of the lithium ion battery, for example, the high-temperature performance can be improved by adding a film-forming additive to passivate the positive and negative electrode interfaces, but the low-temperature performance of the lithium ion battery is seriously deteriorated due to the increase of the impedance of the positive and negative electrode interfaces, and in addition, the increase of the impedance is not favorable for the long-term cycle performance.
In view of the above, it is necessary to develop a nonaqueous electrolyte solution that can achieve both high and low temperature performance and cycle performance of a lithium battery, and a lithium ion battery using the same.
Patent application CN103107355A discloses an electrolyte for lithium ion battery, wherein the branched cyclic ethylene sulfate is mixed with the unbranched cyclic ethylene sulfate or sulfonate to reduce the resistance of the battery and improve the high temperature performance and cycle performance of the battery. However, it is still insufficient in low-temperature discharge performance and high-temperature storage performance, and there is a need for improvement.
Patent application CN103098290A discloses a nonaqueous electrolytic solution in which a cyclic ethylene sulfate having a substituent group of a sulfonyl group is contained in an electrolytic solution to form a film on a negative electrode, thereby improving the capacity maintenance of a battery and significantly suppressing a potential decrease. However, it does not relate to the study of the expansion ratio and the rate discharge characteristic.
Patent application CN107017433B discloses a nonaqueous electrolyte, which comprises a nonaqueous organic solvent, a lithium salt, and an additive, and is beneficial to improving capacity retention rate, discharge capacity and high temperature performance, but the volume expansion rate and internal resistance increase rate are relatively large, which is not beneficial to industrial manufacture and practical application.
Disclosure of Invention
In view of the problems in the background art, an object of the present invention is to provide a nonaqueous electrolyte solution capable of ensuring high-temperature storage performance of a lithium ion battery while significantly improving low-temperature cycle performance, rate discharge performance, and safety performance of the lithium ion battery, and a lithium ion battery using the same.
The invention provides the following technical scheme:
[1] a nonaqueous electrolytic solution comprising a lithium salt, an organic solvent, and an additive comprising an aryl sulfate and a silicon-containing compound,
the aryl sulfate is aryl sulfate shown in formula A,
Figure BDA0003015711610000021
wherein R is1、R2Each independently is phenyl or polycyclic aromatic hydrocarbon group with 2-3 aromatic rings, or R1、R2Can be connected to form phenyl or polycyclic aromatic hydrocarbon with 2-3 aromatic rings; the phenyl or polycyclic aromatic hydrocarbon group with 2-3 aromatic rings can be substituted by one or more of F, Cl, Br, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, carboxylic ester with 1-10 carbon atoms, carbonyl with 1-10 carbon atoms and cyano with 1-10 carbon atoms;
the silicon-containing compound is a silicon-containing compound shown in a formula B,
Figure BDA0003015711610000031
wherein R is3、R4、R5、R6Each independently F, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a carboxylate group having 1 to 10 carbon atoms, and a phenyl group; the alkyl, alkenyl and alkynyl can be substituted by one or more of O, N, S, F, Cl and Br; the phenyl group may be represented by F, Cl,Br, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, carboxylic ester with 1-10 carbon atoms, carbonyl with 1-10 carbon atoms and cyano with 1-10 carbon atoms.
[2] The nonaqueous electrolytic solution of claim 1, wherein the arylsulfate is an arylsulfate represented by the formula A,
Figure BDA0003015711610000032
wherein R is1、R2Each independently is phenyl, biphenyl, naphthyl, phenanthryl; or, R1、R2May be linked to form a phenyl, biphenyl, naphthyl, phenanthryl group; the phenyl, biphenyl, naphthyl and phenanthryl can be substituted by one or more of F, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, methoxy, ethoxy, tert-butoxy, formyl, acetyl, methoxycarbonyl, ethoxycarbonyl, cyano and cyanomethyl.
[3] The nonaqueous electrolytic solution of claim 1, wherein the arylsulfate ester represented by the formula A contains one or more compounds selected from the group consisting of,
Figure BDA0003015711610000041
[4] the nonaqueous electrolytic solution of claim 1, wherein the silicon-containing compound is a silicon-containing compound represented by formula B,
Figure BDA0003015711610000042
wherein R is3、R4、R5、R6Each independently is F, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, vinyl, allyl, ethynyl, formate, acetate, formyl, acetyl, cyano, cyanomethylOr phenyl; the phenyl can be substituted by one or more of F, Cl, Br, methyl, ethyl, isopropyl, tert-butyl, vinyl, allyl, ethynyl, formate, acetate, formyl, acetyl, cyano and cyanomethyl.
[5] The nonaqueous electrolytic solution of claim 1, wherein the silicon-containing compound represented by the formula B contains one or more of the following compounds,
Figure BDA0003015711610000051
[6] the nonaqueous electrolytic solution of any one of claims 1 to 5, wherein the nonaqueous electrolytic solution contains 8.0 to 15.0 parts by mass of a lithium salt, 0.01 to 5.0 parts by mass of an arylsulfuric acid ester represented by formula A, and 0.01 to 5.0 parts by mass of a silicon-containing compound represented by formula B, relative to 70.0 parts by mass of the organic solvent.
[7] The nonaqueous electrolytic solution of claim [6], which comprises a lithium salt, an organic solvent and an additive, wherein the additive comprises an arylsulfate ester, a silicon-containing compound, and fluoroethylene carbonate,
wherein the organic solvent comprises, relative to 70.0 parts of organic solvent, 8.0-15.0 parts of lithium salt, 0.01-5.0 parts of aryl sulfate shown in formula A, 0.01-5.0 parts of silicon-containing compound shown in formula B and 0.01-15.0 parts of fluoroethylene carbonate.
[8] The nonaqueous electrolytic solution of claim [6], which comprises a lithium salt, an organic solvent and an additive comprising an arylsulfate ester, a silicon-containing compound, fluoroethylene carbonate, and other additives,
wherein the organic solvent comprises, relative to 70.0 parts of organic solvent, 8.0-15.0 parts of lithium salt, 0.01-5.0 parts of aryl sulfate shown in formula A, 0.01-5.0 parts of silicon-containing compound shown in formula B, 0.01-15.0 parts of fluoroethylene carbonate and 1.0-5.0 parts of other additives,
the other additive comprises one or more of 1, 3-propane sultone, vinylene carbonate, triallyl isocyanurate, 1, 4-butane sultone, 1, 3-propene sultone, methylene methanedisulfonate, ethoxypentafluorocyclotriphosphazene, tris (trimethylsilyl) phosphate, triallyl phosphate, citraconic anhydride, and tris (trimethylsilyl) borate.
[9]According to claim [1]]The nonaqueous electrolyte solution is characterized in that the lithium salt contains lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium perchlorate (LiClO)4) Lithium bistrifluoromethanesulfonylimide (LiN (CF)3SO2)2) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluoro (LiPO)2F2) And lithium difluorobis (oxalato) phosphate (LiDFOP), preferably lithium hexafluorophosphate and lithium difluorophosphate.
[10] The nonaqueous electrolytic solution of claim 1, wherein the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, butylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl difluoroacetate, difluoroethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran, and 2-methyltetrahydrofuran, and preferably comprises one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate.
[11] A lithium ion battery comprising a nonaqueous electrolytic solution according to any one of claims 1 to 10, a positive electrode sheet, a negative electrode sheet, and a separator. Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the non-aqueous electrolyte contains aryl sulfate with a specific structure and a silicon-containing compound as additives, and further contains fluoroethylene carbonate and the like, the content ratio of the aryl sulfate and the silicon-containing compound is precisely controlled, and the synergistic effect of various additives is exerted, so that the high-temperature storage performance of the lithium ion battery can be improved, and the low-temperature cycle performance, the rate discharge performance, the overcharge resistance and other safety performances of the lithium ion battery are obviously improved.
Detailed Description
The invention provides a nonaqueous electrolyte which is characterized by comprising a lithium salt, an organic solvent and an additive, wherein the additive comprises aryl sulfate and a silicon-containing compound,
the aryl sulfate is aryl sulfate shown in formula A,
Figure BDA0003015711610000071
wherein R is1、R2Each independently is phenyl or polycyclic aromatic hydrocarbon group with 2-3 aromatic rings, or R1、R2Can be connected to form phenyl or polycyclic aromatic hydrocarbon with 2-3 aromatic rings; the phenyl or polycyclic aromatic hydrocarbon group with 2-3 aromatic rings can be substituted by one or more of F, Cl, Br, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, carboxylic ester with 1-10 carbon atoms, carbonyl with 1-10 carbon atoms and cyano with 1-10 carbon atoms;
the silicon-containing compound is a silicon-containing compound shown in a formula B,
Figure BDA0003015711610000081
wherein R is3、R4、R5、R6Each independently F, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a carboxylate group having 1 to 10 carbon atoms, and a phenyl group; the alkyl, alkenyl and alkynyl can be substituted by one or more of O, N, S, F, Cl and Br; the phenyl group can be substituted by F, Cl, Br, C1-10 alkyl group, C atomA substituted one or more of an alkoxy group having 1 to 10 carbon atoms, a carboxylate group having 1 to 10 carbon atoms, a carbonyl group having 1 to 10 carbon atoms, and a cyano group having 1 to 10 carbon atoms.
In the above aryl sulfates, further, R1、R2Each independently is phenyl, biphenyl, naphthyl, phenanthryl; or, R1、R2May be linked to form a phenyl, biphenyl, naphthyl, phenanthryl group; the phenyl, biphenyl, naphthyl and phenanthryl can be substituted by one or more of F, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, methoxy, ethoxy, tert-butoxy, formyl, acetyl, methoxycarbonyl, ethoxycarbonyl, cyano and cyanomethyl.
In the above aryl sulfates, preferably, R1、R2May be linked to form a phenyl, biphenyl, naphthyl, phenanthryl group; the phenyl, biphenyl, naphthyl and phenanthryl can be substituted by one or more of F, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, methoxy, ethoxy, tert-butoxy, formyl, acetyl, methoxycarbonyl, ethoxycarbonyl, cyano and cyanomethyl.
The aryl sulfate shown in the formula A contains one or more than two of the following compounds,
Figure BDA0003015711610000091
the aryl sulfate shown in the formula A is preferably one or more than two of the following compounds,
Figure BDA0003015711610000101
more preferably an arylsulfuric acid ester represented by the formula A1-A8,
Figure BDA0003015711610000102
among the above-mentioned aryl sulfates, there are,more preferably, R1、R2May be linked to form a phenyl, biphenyl, naphthyl, phenanthryl group; the phenyl, biphenyl, naphthyl and phenanthryl can be substituted by one or more of F, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, methoxy, ethoxy, tert-butoxy, formyl, acetyl, methoxycarbonyl, ethoxycarbonyl, cyano and cyanomethyl.
The arylsulfuric acid ester is more preferably a cyclic arylsulfuric acid ester represented by the formulae A1 to A7, and still more preferably a cyclic arylsulfuric acid ester represented by the formulae A1, A3, A4, A5 or A6.
The aryl sulfate shown in the formula A can be reduced at a negative electrode to form a Solid Electrolyte Interface (SEI) film. The aryl sulfate can form a film on a negative electrode, has a compact structure, inhibits the decomposition of a solvent, has higher conductivity, can reduce interfacial impedance, can oxidize the aryl on the positive electrode to form a film to passivate the positive electrode, and has higher oxidation potential than alkyl sulfate, so that the high-temperature storage performance, overcharge resistance and other safety performances of the battery can be improved. However, when the amount of the arylsulfate ester is too large, the film is likely to be too thick, which leads to an increase in battery impedance and deterioration in cycle performance and rate discharge performance; when the addition amount is too small, the film forming effect is not obvious, the improvement effect on the battery performance is small, the high-temperature storage performance is poor, and the overcharge resistance is poor.
In the nonaqueous electrolytic solution, the silicon-containing compound represented by the formula B contains one or more of the following compounds,
Figure BDA0003015711610000111
the silicon-containing compound represented by the formula B is preferably a silicon-containing compound represented by the following formulae B1 to B7, the silicon-containing compound represented by the formula B is preferably a silicon compound containing both an unsaturated bond and a heteroatom such as N, O, S, and more preferably the following formulae B1, B2, B3, B5, and B7.
Figure BDA0003015711610000121
The silicon-containing compound shown in the formula B can be preferentially reduced to form a film on a negative electrode, and the reduction and gas generation of a solvent are inhibited. Si may be reacted with F-Complexing, O, N, S heteroatoms may be with H+Complexing, reducing the damage of HF to the positive electrode and the negative electrode, and improving the high-temperature storage property and the cycle performance of the battery. However, when the usage amount of the silicon-containing compound is too much, the film formed on the negative electrode is too thick, so that the impedance of the battery is increased, and the cycle performance and the rate discharge performance are influenced; when the amount of the catalyst is too small, the high-temperature storage property is deteriorated and the expansion of the produced gas cannot be suppressed.
The nonaqueous electrolyte solution contains, by mass, 70.0 parts of an organic solvent, 8.0 to 15.0 parts of a lithium salt, 0.01 to 5.0 parts of an arylsulfuric acid ester represented by the formula A, and 0.01 to 5.0 parts of a silicon-containing compound represented by the formula B.
Further, the nonaqueous electrolyte solution contains, by mass, 8.0 to 15.0 parts of a lithium salt, preferably 10.5 to 15.0 parts of a lithium salt, and more preferably 13.0 to 15.0 parts of a lithium salt, relative to 70.0 parts of an organic solvent.
Further, the nonaqueous electrolytic solution contains 0.01 to 5.0 parts by mass of an arylsulfuric acid ester represented by the formula A, preferably 0.1 to 5.0 parts by mass of an arylsulfuric acid ester represented by the formula A, and more preferably 1.0 to 3.0 parts by mass of an arylsulfuric acid ester represented by the formula A, relative to 70.0 parts by mass of an organic solvent.
Further, the nonaqueous electrolytic solution contains 0.01 to 5.0 parts by mass of a silicon-containing compound represented by the formula B, preferably 0.1 to 5.0 parts by mass of a silicon-containing compound represented by the formula B, and more preferably 0.1 to 0.5 part by mass of a silicon-containing compound represented by the formula B, relative to 70.0 parts by mass of an organic solvent.
The unsaturated bond of the silicon-containing compound has low reduction potential, is preferentially reduced to form a film on the negative electrode, and can inhibit the reduction and gas production of the solvent component of the electrolyte on the negative electrode.
Preferably, in the above nonaqueous electrolytic solution, a lithium salt, an organic solvent and an additive are contained, the additive containing an arylsulfate, a silicon-containing compound, and fluoroethylene carbonate,
wherein the organic solvent comprises, relative to 70.0 parts of organic solvent, 8.0-15.0 parts of lithium salt, 0.01-5.0 parts of aryl sulfate shown in formula A, 0.01-5.0 parts of silicon-containing compound shown in formula B and 0.01-15.0 parts of fluoroethylene carbonate.
Further, in the nonaqueous electrolytic solution, the additive further contains 0 to 15.0 parts by mass of fluoroethylene carbonate, preferably 1.0 to 15.0 parts by mass of fluoroethylene carbonate, more preferably 3.0 to 15.0 parts by mass of fluoroethylene carbonate, and more preferably 3.0 to 12.0 parts by mass of fluoroethylene carbonate, relative to 70.0 parts by mass of the organic solvent.
The fluoroethylene carbonate can be reduced to form a film at a negative electrode, the film forming impedance is low, a formed solid electrolyte interface film (SEI film) is compact, the cycle performance of the battery, particularly the cycle performance at normal temperature, can be improved, the low-temperature discharge performance and the rate discharge performance can be improved, and the electric conductivity of the negative electrode SEI film formed by the fluoroethylene carbonate is high. However, when the amount of the catalyst is too large, the gas is generated at high temperature seriously, and when the amount is too small, the film formation of the negative electrode is unstable, and the cycle performance and the discharge performance are deteriorated.
Preferably, in the above nonaqueous electrolytic solution, a lithium salt, an organic solvent and an additive are contained, the additive contains aryl sulfate, a silicon-containing compound, fluoroethylene carbonate, and other additives,
wherein the organic solvent comprises, relative to 70.0 parts of organic solvent, 8.0-15.0 parts of lithium salt, 0.01-5.0 parts of aryl sulfate shown in formula A, 0.01-5.0 parts of silicon-containing compound shown in formula B, 0.01-15.0 parts of fluoroethylene carbonate and 1.0-5.0 parts of other additives,
the other additive comprises one or more of 1, 3-propane sultone, vinylene carbonate, triallyl isocyanurate, 1, 4-butane sultone, 1, 3-propene sultone, methylene methanedisulfonate, ethoxy pentafluorocyclotriphosphazene, tris (trimethylsilyl) phosphate, triallyl phosphate, citraconic anhydride, and tris (trimethylsilyl) borate, and preferably one or more of 1, 3-propane sultone, vinylene carbonate, triallyl isocyanurate.
The other additives are matched with aryl sulfate and a silicon-containing compound for use, so that the high-temperature storage and cycle performance of the battery can be further improved, for example, 1, 3-propane sultone can form a film on the positive electrode to protect the positive electrode, vinylene carbonate is reduced on the negative electrode to form a compact protective film, a triallyl isocyanurate unsaturated bond can be reduced on the negative electrode to form a film, and the ureide structure of the triallyl isocyanurate unsaturated bond has a stabilizing effect on the positive electrode.
Further, in the nonaqueous electrolytic solution, the lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium perchlorate (LiClO)4) Lithium bistrifluoromethanesulfonylimide (LiN (CF)3SO2)2) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluoro (LiPO)2F2) And lithium difluorobis (oxalato) phosphate (LiDFOP), preferably lithium hexafluorophosphate, lithium difluorophosphate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium bis (fluorosulfonyl) imide, and more preferably lithium hexafluorophosphate and lithium difluorophosphate. The mixing ratio of each lithium salt in the lithium salt composition used in the present invention is not particularly limited as long as a predetermined effect can be achieved.
Further, in the nonaqueous electrolytic solution, the organic solvent includes one or more of ethylene carbonate, propylene carbonate, butylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl difluoroacetate, difluoroethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran, and 2-methyltetrahydrofuran, and preferably includes one or more of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, and diethyl carbonate. The blending ratio of each solvent in the solvent composition used in the present invention is not particularly limited as long as a predetermined effect can be achieved.
The invention also provides a lithium ion battery, which is characterized by comprising the non-aqueous electrolyte, a positive plate, a negative plate and a diaphragm, wherein the non-aqueous electrolyte is the non-aqueous electrolyte.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
In the synthesis example of the invention, the raw material reagent is an analytical pure product of an avastin chemical reagent and a Meclin chemical reagent, a solvent is purchased from Tatan great, and water is prepared by a water purifier. Lithium salt of electrolyte raw materials is purchased from polyfluoro multi-chemical industry Co., Ltd, organic solvent is purchased from Su Wen electronic materials Co., Ltd, fluoroethylene carbonate is purchased from Jiangsu Huasheng lithium materials Co., Ltd, ethylene sulfate is purchased from Fujian Xin scientific and technological development Co., Ltd, aryl sulfate is self-made, and silicon-containing compounds are analytically pure products of an Aratin chemical reagent and a Meclin chemical reagent and are used after water is removed to below 20 ppm. The battery material nickel cobalt lithium manganate is purchased from Ningbo capacity hundred new energy science and technology corporation, the cathode silica material is purchased from Beibei new energy material corporation, and the diaphragm is purchased from Shenzhen city star source material science and technology corporation. The method for producing a lithium ion battery and the method for synthesizing an arylsulfate compound in an electrolyte according to the present invention will be described below.
Example 1
Preparation of nonaqueous electrolyte
At water content<In a 10ppm argon atmosphere glove box, after 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 30.0 parts by mass of diethyl carbonate (DEC), and 15.0 parts by mass of Ethyl Methyl Carbonate (EMC) were uniformly mixed, the temperature was controlled to 15 ℃, and 12.5 parts by mass of lithium hexafluorophosphate (LiPF) was added6) And 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) Dissolving in the organic solvent, and adding 1.0 part by mass of aryl sulfate represented by formula A1, 5.0 parts by mass of fluoroethylene carbonate, 0.2 part by mass of a silicon-containing compound represented by formula B1,And 3.0 parts by mass of triallyl isocyanurate, and the mixture was stirred at 200rpm for 30 minutes by a stirrer until uniform, to obtain a nonaqueous electrolytic solution of example 1.
Synthesis of aryl sulfate A1
11.01g (0.1mol) of catechol was dissolved in 200.00g of 1, 2-dichloroethane, and 19.78g (0.25mol) of pyridine was charged in a 200mL reactor, and 14.85g (0.11mol) of sulfuryl chloride was added thereto, and the reaction was carried out at 0 ℃ for 6 hours. After the reaction, the reaction solution was filtered. The filtrate was washed with water (200 mL. times.3). After standing and separating, the organic phase is concentrated to obtain crude aryl sulfate A1. The crude product of A1 was dissolved in 1 times the mass of dimethyl carbonate, dried with 4A molecular sieves to remove water, crystallized at-10 deg.C, filtered to give crystals of A1, and dried under vacuum to give 13.76g of arylsulfonate A1 (yield 80%), water content 34ppm, acid value (in terms of HF) 8.1ppm, purity GC 99.95%.
Figure BDA0003015711610000161
Preparation of lithium ion battery
(1) Preparation of positive plate
The preparation method comprises the following steps of (1) mixing a positive active material nickel cobalt lithium manganate (NCM811), a conductive agent SuperP, a carbon nano tube and a binder polyvinylidene fluoride (PVDF) according to a mass part ratio of 97: 1: 0.5: 1.5 and N-methyl pyrrolidone (NMP) are evenly mixed to prepare anode slurry, the anode slurry is coated on a current collector aluminum foil according to the thickness of 100 mu m, the aluminum foil is dried at 70 ℃, cold pressing is carried out at the room temperature of 4Mpa, and then the anode plate is prepared by welding lugs after edge cutting, sheet cutting and strip dividing.
(2) Preparation of negative plate
Mixing a negative active material silica (SiO450), a conductive agent SuperP, a thickening agent CMC and a binding agent SBR according to a mass ratio of 97: 1.0: 1.0: 1.5 mixing with purified water to prepare negative electrode slurry, coating the slurry on a current collector copper foil according to the thickness of 100 mu m, drying at 70 ℃, cold pressing at 4Mpa at room temperature, then trimming, cutting into pieces, slitting, welding a tab and preparing a negative electrode piece.
(3) Assembly of lithium ion batteries
Taking a PE porous polymer film as a diaphragm, sequentially laminating the prepared positive plate, the diaphragm and the prepared negative plate to enable the diaphragm to be positioned between the positive plate and the negative plate, and winding to obtain a bare cell; placing the bare cell in an aluminum plastic shell package under vacuum pressure of-0.95 × 105Drying at 100 ℃ under Pa until the water content is below 100 ppm. And (3) injecting the prepared nonaqueous electrolyte into the dried bare cell, packaging, standing, forming (0.02C constant current charging for 2h and 0.1C constant current charging for 2h), shaping, and testing capacity to prepare the soft package lithium ion battery.
Example 2
A nonaqueous electrolyte solution and a lithium ion battery were prepared by referring to the method of example 1, except that the additives were 1.0 part by mass of the arylsulfate represented by the formula A2, 5.0 parts by mass of fluoroethylene carbonate, and 0.2 part by mass of the silicon-containing compound represented by the formula B4 when the nonaqueous electrolyte solution was prepared.
Synthesis of aryl sulfate A2
16.62g (0.1mol) of p-tert-butylcatechol was dissolved in 200.00g of 1, 2-dichloroethane, and 19.78g (0.25mol) of pyridine was added to a 200mL reactor, and 14.85g (0.11mol) of sulfuryl chloride was further added to the reactor, and the reaction was carried out at 0 ℃ for 6 hours. After the reaction, the reaction solution was filtered. The filtrate was washed with water (200 mL. times.3). After standing and separating, the organic phase is concentrated to obtain crude aryl sulfate A2. The crude product of A2 was dried over 4A molecular sieves with removal of water and distilled under reduced pressure to give 18.72g of arylsulfate A2 (yield 82%), moisture 30ppm, acid number (in terms of HF) 8.5ppm, purity GC 99.95%.
Figure BDA0003015711610000171
Example 3
A nonaqueous electrolyte solution and a lithium ion battery were prepared by referring to the method of example 1, except that the additives were 1.0 part by mass of the arylsulfate represented by the formula A3, 5.0 parts by mass of fluoroethylene carbonate, and 0.2 part by mass of the silicon-containing compound represented by the formula B5 when the nonaqueous electrolyte solution was prepared.
Synthesis of aryl sulfate A3
12.81g (0.1mol) of 4-fluorocatechol was dissolved in 200.00g of 1, 2-dichloroethane, 19.78g (0.25mol) of pyridine was charged in a 200mL reactor, 14.85g (0.11mol) of sulfuryl chloride was further added, and the reaction was carried out at 0 ℃ for 6 hours. After the reaction, the reaction solution was filtered. The filtrate was washed with water (200 mL. times.3). After standing and separating, the organic phase is concentrated to obtain a crude product of aryl sulfate A3. The crude product of A3 was dried over 4A molecular sieves with removal of water and distilled under reduced pressure to give 16.16g of an arylsulfate A3 (yield 85%), moisture 31ppm, acid value (in terms of HF) 8.8ppm, purity GC 99.95%.
Figure BDA0003015711610000181
Example 4
A nonaqueous electrolyte solution and a lithium ion battery were prepared by referring to the method of example 1, except that the additives were 0.1 part by mass of the arylsulfate represented by the formula A4, 5.0 parts by mass of fluoroethylene carbonate, and 0.2 part by mass of the silicon-containing compound represented by the formula B2 when the nonaqueous electrolyte solution was prepared.
Synthesis of aryl sulfate A4
Methyl 3, 4-dihydroxybenzoate 16.81g (0.1mol) was dissolved in 1, 2-dichloroethane 200.00g, pyridine 19.78g (0.25mol) was charged into a 200mL reactor, sulfuryl chloride 14.85g (0.11mol) was further added, and the reaction was carried out for 6 hours while controlling the temperature at 0 ℃. After the reaction, the reaction solution was filtered. The filtrate was washed with water (200 mL. times.3). After standing and separating, the organic phase is concentrated to obtain crude aryl sulfate A4. The crude product of A4 was dried over 4A molecular sieves with removal of water and distilled under reduced pressure to give 18.65g of aryl sulfate A4 (yield 81%), moisture 40ppm, acid number (in terms of HF) 9ppm, purity GC 99.95%.
Figure BDA0003015711610000191
Example 5
A nonaqueous electrolyte solution and a lithium ion battery were produced by referring to the method in example 1, except that the additives were 2.0 parts by mass of the aryl sulfate represented by formula A5, 5.0 parts by mass of fluoroethylene carbonate, 0.2 parts by mass of the silicon-containing compound represented by formula B3, and 1.0 part by mass of vinylene carbonate in the production of the nonaqueous electrolyte solution.
Synthesis of aryl sulfate A5
13.51g (0.1mol) of 3, 4-dihydroxybenzonitrile was dissolved in 200.00g of 1, 2-dichloroethane, 19.78g (0.25mol) of pyridine was charged into a 200mL reactor, 14.85g (0.11mol) of sulfuryl chloride was further added thereto, and the reaction was carried out for 6 hours while controlling the temperature at 0 ℃. After the reaction, the reaction solution was filtered. The filtrate was washed with water (200 mL. times.3). After standing and separating, the organic phase is concentrated to obtain crude aryl sulfate A5. The crude product of A5 was dried by 4A molecular sieves to remove water and distilled under reduced pressure to give 15.77g of arylsulfate A5 (yield 80%), having a water content of 45ppm, an acid number (as HF) of 7.5ppm and a purity GC of 99.95%.
Figure BDA0003015711610000192
Example 6
A nonaqueous electrolyte solution and a lithium ion battery were prepared by the method of example 1, except that the additives were 5.0 parts by mass of the arylsulfate represented by the formula A6, 5.0 parts by mass of fluoroethylene carbonate, and 0.2 parts by mass of the silicon-containing compound represented by the formula B6.
Synthesis of aryl sulfate A6
21.82g (0.1mol) of [1, 1-diphenyl ] -2,2,3, 3-tetraol was dissolved in 200.00g of 1, 2-dichloroethane, 19.78g (0.25mol) of pyridine was charged in a 200mL reactor, 29.70g (0.22mol) of sulfuryl chloride was further added, and the reaction was carried out for 6 hours while controlling the temperature to 0 ℃. After the reaction, the reaction solution was filtered. The filtrate was washed with water (200 mL. times.3). After standing and separating, the organic phase is concentrated to obtain crude aryl sulfate A1. The crude product of A6 was dissolved in 1 times the mass of dimethyl carbonate, dried with 4A molecular sieves to remove water, crystallized at-10 deg.C, filtered to give crystals of A6, and dried under vacuum to give 28.41g of arylsulfate A6 (yield 83%), moisture 43ppm, acid number (as HF) 8.5ppm, purity HPLC 99.95%.
Figure BDA0003015711610000201
Example 7
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the additives were 2.0 parts by mass of an arylsulfate ester represented by the formula A7, 5.0 parts by mass of fluoroethylene carbonate, 0.1 part by mass of a silicon-containing compound represented by the formula B7, and 5.0 parts by mass of 1, 3-propanesultone in the production of the nonaqueous electrolytic solution.
Synthesis of aryl sulfate A7
15.21g (0.2mol) of 3, 4-dihydroxyacetophenone was dissolved in 200.00g of 1, 2-dichloroethane, 19.78g (0.25mol) of pyridine was charged in a 200mL reactor, 14.85g (0.11mol) of sulfuryl chloride was further added, and the reaction was carried out at 0 ℃ for 6 hours. After the reaction, the reaction solution was filtered. The filtrate was washed with water (200 mL. times.3). After standing and separating, the organic phase is concentrated to obtain crude aryl sulfate A1. The crude product of A6 was distilled under reduced pressure to give 17.77g of arylsulfonate A7 (yield 83%), moisture 30ppm, acid value (in terms of HF) 8.2ppm, purity GC 99.95%.
Figure BDA0003015711610000211
Example 8
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the additive was 0.1 part by mass of the arylsulfate represented by the formula A8 and 0.5 part by mass of the silicon-containing compound represented by the formula B1 in producing the nonaqueous electrolytic solution.
Synthesis of aryl sulfate A8
27.62g (0.2mol) of 3, 4-methylenedioxyphenol was dissolved in 200.00g of 1, 2-dichloroethane, 19.78g (0.25mol) of pyridine was charged in a 200mL reactor, 14.85g (0.11mol) of sulfuryl chloride was further added, and the reaction was carried out for 6 hours while controlling the temperature at 0 ℃. After the reaction, the reaction solution was filtered. The filtrate was washed with water (200 mL. times.3). After standing and separating, the organic phase is concentrated to obtain crude aryl sulfate A1. The crude product of A8 was dissolved in 1 times the mass of dimethyl carbonate, dried with 4A molecular sieves to remove water, crystallized at-10 deg.C, filtered to give crystals of A8, and dried under vacuum to give 28.41g of arylsulfate A8 (yield 84%), water content 33ppm, acid number (in terms of HF) 8.8ppm, purity GC 99.95%.
Figure BDA0003015711610000212
Example 9
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the additive was 1.0 part by mass of the arylsulfate ester represented by the formula A1 and 5.0 parts by mass of the silicon-containing compound represented by the formula B2 at the time of production of the nonaqueous electrolytic solution.
Example 10
A nonaqueous electrolyte solution and a lithium ion battery were produced by referring to the method of example 1, except that, in the production of the nonaqueous electrolyte solution, the organic solvent was 15.0 parts by mass of Ethylene Carbonate (EC), 10 parts by mass of Propylene Carbonate (PC), 35.0 parts by mass of diethyl carbonate (DEC), and 10.0 parts by mass of Ethyl Methyl Carbonate (EMC), and the lithium salt was 10.0 parts by mass of lithium hexafluorophosphate (LiPF)6) And 0.5 part by mass of lithium bis (fluorosulfonyl) imide (LiFSI), 1.0 part by mass of an aryl sulfate represented by formula A1, 3.0 parts by mass of fluoroethylene carbonate, and 0.2 part by mass of a silicon-containing compound represented by formula B1.
Example 11
A nonaqueous electrolyte solution and a lithium ion battery were prepared by referring to the method of example 1, except that, in the preparation of the nonaqueous electrolyte solution, the organic solvent was 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 30.0 parts by mass of diethyl carbonate (DEC), and 15.0 parts by mass of Ethyl Methyl Carbonate (EMC), and the lithium salt was 14.5 parts by mass of lithium hexafluorophosphate (LiPF)6) And 0.5 part by mass of lithium tetrafluoroborate (LiBF)4) The additives were 1.0 part by mass of an aryl sulfate represented by the formula A3, 12.0 parts by mass of fluoroethylene carbonate, and 5.0 parts by mass of a silicon-containing compound represented by the formula B5.
Example 12
A nonaqueous electrolyte solution and a lithium ion battery were prepared by referring to the method of example 1, except that, in the preparation of the nonaqueous electrolyte solution, the organic solvent was 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 35.0 parts by mass of diethyl carbonate (DEC), and 10.0 parts by mass of Ethyl Methyl Carbonate (EMC), and the lithium salt was 7.5 parts by mass of lithium hexafluorophosphate (LiPF)6) And 0.5 part by mass of lithium difluorooxalato borate (LiDFOB), the additives being 1.0 part by mass of an arylsulfate represented by the formula A1, 15.0 parts by mass of fluoroethylene carbonate, and 0.2 part by mass of a silicon-containing compound represented by the formula B1.
Comparative example 1
A nonaqueous electrolyte solution and a lithium ion battery were prepared by referring to the method of example 1, except that, in the preparation of the nonaqueous electrolyte solution, the organic solvent was 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 35.0 parts by mass of diethyl carbonate (DEC), and 10.0 parts by mass of Ethyl Methyl Carbonate (EMC), and the lithium salt was 10.0 parts by mass of lithium hexafluorophosphate (LiPF)6)And 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additives were 1.0 part by mass of an aryl sulfate represented by the formula A1 and 12.0 parts by mass of fluoroethylene carbonate.
Comparative example 2
A nonaqueous electrolyte solution and a lithium ion battery were prepared by referring to the method of example 1, except that, in the preparation of the nonaqueous electrolyte solution, the organic solvent was 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 30.0 parts by mass of diethyl carbonate (DEC), and 15.0 parts by mass of Ethyl Methyl Carbonate (EMC), and the lithium salt was 8.0 parts by mass of lithium hexafluorophosphate (LiPF)6) And 0.01 part by mass of lithium difluorophosphate (LiPO)2F2) The additives were 1.0 part by mass of an aryl sulfate represented by formula A2 and 0.5 part by mass of fluoroethylene carbonate.
Comparative example 3
A nonaqueous electrolytic solution and a lithium ion battery were prepared by referring to the method of example 1, except that, in the preparation of the nonaqueous electrolytic solution, the organic solvent was 15.0 parts by mass of Ethylene Carbonate (EC), 10.0 parts by mass of Propylene Carbonate (PC), 30.0 parts by mass of diethyl carbonate (DEC), and 15.0 parts by mass of Ethyl Methyl Carbonate (EMC), and the lithium salt was 8.0 parts by mass of hexafluoro chlorideLithium phosphate (LiPF)6) And 1.0 part by mass of lithium difluorophosphate (LiPO)2F2) The additives were 1.0 part by mass of an aryl sulfate represented by formula A3 and 0.1 part by mass of fluoroethylene carbonate.
Comparative example 4
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additive was 0.1 part by mass of an aryl sulfate represented by the formula A4.
Comparative example 5
A nonaqueous electrolyte solution and a lithium ion battery were produced by referring to the method in example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) in producing the nonaqueous electrolyte solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additive was 2.0 parts by mass of an aryl sulfate represented by the formula A5.
Comparative example 6
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additive was 3.0 parts by mass of an aryl sulfate represented by the formula A6.
Comparative example 7
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was only 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) The additive was only 5.0 parts by mass of fluoroethylene carbonate.
Comparative example 8
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additive was only 5.0 parts by mass of fluoroethylene carbonate.
Comparative example 9
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additives were 1.0 part by mass of ethylene sulfate, 0.2 part by mass of a silicon-containing compound represented by formula B1, and 5.0 parts by mass of fluoroethylene carbonate.
Comparative example 10
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additives were 6.0 parts by mass of an arylsulfate ester represented by the formula A1, 0.2 part by mass of a silicon-containing compound represented by the formula B1, and 5.0 parts by mass of fluoroethylene carbonate.
Comparative example 11
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additives were 0.01 part by mass of the silicon-containing compound represented by formula B7 and 5.0 parts by mass of fluoroethylene carbonate.
Comparative example 12
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) And 0.5 part by mass of a silicon-containing compound represented by the formula B1 as an additive.
Comparative example 13
A nonaqueous electrolytic solution and a lithium ion battery were produced by referring to the method of example 1, except that the lithium salt was 12.5 parts by mass of lithium hexafluorophosphate (LiPF) at the time of producing the nonaqueous electrolytic solution6) 0.5 part by mass of lithium difluorophosphate (LiPO)2F2) The additives were 6.0 parts by mass of the silicon-containing compound represented by formula B2 and 5.0 parts by mass of fluoroethylene carbonate.
The aryl sulfates and silicon-containing compounds used in examples 1 to 12 and comparative examples 1 to 13 are as follows:
Figure BDA0003015711610000251
the structure of the ethylene sulfate is
Figure BDA0003015711610000252
In table 1, EC represents ethylene carbonate, PC represents propylene carbonate, DEC represents diethyl carbonate, and EMC represents ethyl methyl carbonate. The compositions of the nonaqueous electrolytic solutions of examples 1 to 15 and comparative examples 1 to 13 are shown in Table 1.
TABLE 1
Figure BDA0003015711610000261
The following describes the test procedure and test results of the lithium ion battery.
1. And (3) low-temperature discharge performance test:
the initially adjusted cell was charged at constant current and constant voltage of 0.33C to 4.2V at 25 ℃, the current was cut off at 0.02C, left for 5min, discharged at 0.33C to 2.5V at 25 ℃, the cell discharge capacity at 25 ℃ was recorded, left for 5 min. Charging to 4.2V at constant current and constant voltage of 0.33C, cutting off current of 0.02C, placing the battery in a low-temperature box at minus 10 ℃ for 5h, discharging to 2.5V at 0.33C, and recording the discharge capacity at minus 10 ℃.
-10 ℃ discharge capacity retention (%) -10 ℃ discharge capacity/25 ℃ discharge capacity × 100%
2. And (3) rate discharge performance test:
the initially conditioned cells were charged at constant current and constant voltage at 0.33C to 4.2V, current cut-off 0.02C, left at 25 ℃ for 5min, discharged at 0.33C to 2.5V at 25 ℃, and the cell discharge capacity at 0.33C was recorded and left at 5 min. Charging to 4.2V at constant current and constant voltage of 0.33C, cutting off current of 0.02C, standing for 5min, discharging to 2.5V at 3C, and recording the 3C discharge capacity.
The 3C discharge capacity retention (%) -3C discharge capacity/0.33C discharge capacity × 100%
3. And (3) testing the high-temperature storage performance:
firstly, charging the initially adjusted battery to 4.2V at a constant current and a constant voltage of 0.33C and stopping the current at 0.02C at 25 ℃, standing for 5min, discharging the battery to 2.5V at 0.33C, and recording the discharge capacity C0 before the battery is stored. Then charging the battery to a full state of 4.2V at a constant current and a constant voltage of 0.33C, measuring the volume V0 of the battery before high-temperature storage by using a drainage method, then placing the battery in a constant temperature box at 60 ℃ for storage for 7 days, taking out the battery after storage, placing the battery for 12h at 25 ℃ and measuring the volume V1 after storage, and calculating the thickness expansion rate of the battery after the battery is stored for 7 days at the constant temperature of 60 ℃; the cell was discharged to 2.5V at 0.33C constant current, left for 5min and the discharge capacity C1 was recorded. Then, the charge and discharge were cycled 2 times at 0.33C, and the highest one-time discharge capacity was recorded as C2. And (3) calculating the capacity residual rate and the capacity recovery rate of the battery after being stored for 7 days at the constant temperature of 60 ℃, wherein the calculation formula is as follows:
the battery volume expansion rate after 7 days of storage at 60 ═ (V1-V0)/V0 × 100%;
capacity remaining rate after 7 days of storage at 60 ═ C1/C0 × 100%;
4. and (3) testing the normal-temperature cycle performance:
charging the initially adjusted battery to 4.2V at constant current and constant voltage of 0.5C and stopping current of 0.02C at 25 deg.C, standing for 5min, and discharging to 2.5V at constant current of 1C, and standing for 5 min. According to the cycle, after 500 cycles of charge/discharge, the capacity retention rate of the 500 th cycle is calculated, and the calculation formula is as follows:
the 500 th cycle capacity retention ratio (%) (500 th cycle discharge capacity/first cycle discharge capacity) × 100%.
5. And (3) testing high-temperature cycle performance:
firstly, charging the battery after initial adjustment to 4.2V at a constant current and a constant voltage of 0.33C and stopping the current at 0.02C at 25 ℃, standing for 5min, discharging the battery to 2.5V at 0.33C, and recording the initial discharge capacity of the battery. And (3) placing the battery in a high-temperature box at 45 ℃, charging the battery to 4.2V at a constant current and a constant voltage of 0.33C, standing for 5min, discharging the battery to 2.5V at 0.33C, standing for 5min, circulating according to the above, and calculating the capacity retention rate of the battery in 500 cycles after 500 cycles of charging/discharging. The calculation formula is as follows:
the 500 th cycle capacity retention ratio (%) (500 th cycle discharge capacity/first cycle discharge capacity) × 100%.
6. Overcharge test:
the initially adjusted cell was charged at a constant current of 0.33C and a constant voltage to 4.2V at 25 ℃ and the current was cut off at 0.02C, and left for 5 min. The battery was charged to 6V at 1C, and the appearance of the battery was observed within 30 min. The results are reported below:
l0: intact, L1: leakage, L2: flash, L3: luminescence, L4: smoke, L5: on fire, L6: explosion of the vessel
The specific results of the tests are shown in table 2.
TABLE 2
Figure BDA0003015711610000291
From tables 1 and 2, as a result of comparing examples 1 to 12 with comparative examples 1 to 8, it can be seen that the expansion rate of the lithium ion battery becomes large because of the absence of the silicon-containing compound in comparative examples 1 to 8, which indicates that the addition of the silicon-containing compound can suppress the expansion of the lithium ion battery. The possible mechanism is that the unsaturated bond in the silicon-containing compound has low reduction potential and is preferentially reduced to form a film on the negative electrode, so that fluoroethylene carbonate and electrolyte solvent components are inhibited from generating gas by reduction on the negative electrode, and the volume expansion rate is reduced.
From tables 1 and 2, comparing the examples 1 to 12 with the comparative example 9, it can be seen that the high temperature storage property, the high temperature discharge property and the overcharge resistance of the comparative example 9 are poor because the aryl sulfate is used in each example and the ethylene sulfate is used in the comparative example 9. The possible mechanism is that the aryl sulfate has a benzene ring structure, the oxidation potential is higher than that of ethylene sulfate, the oxidation resistance is more excellent, and the benzene ring is oxidized and polymerized on the positive electrode in a small amount to play a role in stabilizing the positive electrode structure, so that the high-temperature storage performance and the overcharge resistance of the battery are improved.
From tables 1 and 2, comparing the examples 8 and 9 with the comparative example 12, it can be seen that the high temperature storage property, the discharge property, the cycle property and the overcharge resistance of the comparative example 12 are remarkably poor since the arylsulfate is used in the examples 8 and 9 and the arylsulfate is not used in the comparative example 12. The possible mechanism is that the aryl sulfate can improve the high-temperature storage performance of the battery, a compact lithium sulfonate or organic lithium sulfonate film layer is formed after reduction, the high conductivity is kept while the negative electrode is protected, and the cycle performance, the low-temperature discharge performance and the rate discharge performance of the battery are improved.
As is apparent from tables 1 and 2, comparing the examples 1 to 7 and 10 to 12 with the comparative example 10, the discharge performance and the cycle performance were poor because 6.0 parts of the arylsulfuric acid ester represented by the formula A was contained in the comparative example 10 with respect to 70 parts of the organic solvent, which is out of the preferable range of the present invention. The mechanism may be that when the amount of the arylsulfate ester added is too large, the film is too thick, which tends to increase the battery impedance and deteriorate the discharge performance and cycle performance.
According to tables 1 and 2, comparative examples 1 to 6 and comparative examples 7 and 8 are compared and analyzed, and it is understood that no silicon-containing compound is used in comparative examples 1 to 8, and fluoroethylene carbonate is not used in comparative examples 4 to 6, but the aryl sulfate of the present invention is used in comparative examples 1 to 6, so that the high-temperature storage performance, the cycle performance and the discharge performance of the lithium ion battery are superior to those of comparative examples 7 and 8, and the volume expansion rate and the overcharge resistance of the lithium ion battery are superior to those of comparative examples 7 and 8. The possible mechanism is that the non-aqueous electrolyte contains aryl sulfate, the aryl sulfate can form a film on a negative electrode to inhibit the decomposition of a solvent, and can be oxidized to form a film on a positive electrode to protect the positive electrode, the aryl sulfate is reduced to form a compact lithium sulfonate or organic lithium sulfonate film layer, the negative electrode is protected, the high conductivity is kept, and the cycle performance, the low-temperature discharge performance and the rate discharge performance of the battery are improved.
From tables 1 and 2, comparative example 7 and comparative example 8 were compared and analyzed, and it was found that the addition of lithium difluorophosphate (LiPO2F2) as a lithium salt partially reduced the expansion rate of the battery at high temperatures. The fluoroethylene carbonate (FEC) decomposes to generate gas at high temperature to cause battery swelling, and the addition of lithium difluorophosphate can partially inhibit the gas generation, thereby reducing the battery swelling rate at high temperature and improving the battery capacity retention rate.
From tables 1 and 2, comparative examples 1,2 and 3 and comparative examples 4, 5 and 6 were compared and analyzed, and it was found that the normal temperature cycle performance, the low temperature discharge performance and the rate discharge performance were slightly superior because fluoroethylene carbonate (FEC) was contained in comparative examples 1,2 and 3. This shows that the addition of fluoroethylene carbonate (FEC) can improve the cycle performance of the battery, particularly the cycle performance at normal temperature, and can partially improve the low-temperature discharge performance and the rate discharge performance. A possible mechanism is that the negative electrode electrolyte interface film (SEI film) formed by participation of fluoroethylene carbonate has low conductivity.
From tables 1 and 2, comparative example 11 and comparative example 12 were compared and analyzed, and it was found that in comparative example 11, the high-temperature storage property was deteriorated and the inhibition of gassing expansion was difficult due to the use of the silicon-containing compound in an excessively small amount.
Comparative example 13 and comparative example 12 were compared and analyzed according to tables 1 and 2, and it was found that in comparative example 13, the film formation at the negative electrode was too thick due to the excessive use of the silicon-containing compound, the battery resistance was increased, the cycle performance was adversely affected, and the low-temperature discharge performance and the rate discharge performance tended to be deteriorated.
From tables 1 and 2, as a result of comparative analysis of examples 1 to 12 and comparative examples 1 to 13, it was found that by using the lithium salt, the organic solvent, the arylsulfate ester, the silicon-containing compound and/or the fluoroethylene carbonate of the present invention in combination in a specific content range in the nonaqueous electrolytic solution of the present invention, the synergistic effect of each component is sufficiently exerted, thereby improving the cycle performance and discharge performance of the battery, improving the high-temperature storage performance and overcharge resistance of the battery, and reducing the volume expansion ratio. The possible mechanism is that the unsaturated bond in the silicon-containing compound has low reduction potential and is preferentially reduced to form a film on the negative electrode, so that the fluoroethylene carbonate and the electrolyte solvent component are inhibited from being reduced to generate gas on the negative electrode, and the volume expansion rate is reduced; the aryl sulfate is reduced to form a compact lithium sulfonate or organic lithium sulfonate film, so that the cathode is protected, the high conductivity is kept, and the cycle performance, the low-temperature discharge performance and the rate discharge performance of the battery are improved; in addition, the aryl sulfate has higher oxidation potential than alkyl sulfate, and can improve the high-temperature storage performance, overcharge resistance and other safety performances of the battery; in addition, both the aryl sulfate and the silicon-containing compound containing unsaturated bonds can be reduced to form a film on the negative electrode, the composite film formed by the aryl sulfate and the silicon-containing compound containing unsaturated bonds is compact, the negative electrode structure can be effectively protected, flatulence generated by the embedding and reduction of solvent components and HF corrosion generated by the decomposition of lithium hexafluorophosphate at high temperature can be prevented, meanwhile, the conductivity is low, and the cycle performance and the discharge performance of the battery can be improved.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
In examples 1 to 15 and comparative examples 1 to 13, only ethylene carbonate, propylene carbonate, diethyl carbonate and methyl ethyl carbonate were used as the organic solvent, but butylene carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl difluoroacetate, difluoroethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran and 2-methyltetrahydrofuran, and the like, can be used as the organic solvent in the reaction for preparing the electrolyte solution of the present invention, and are the same in action and technical effects as those used as the organic solvent in the examples, and thus are suitable for the present invention.
In examples 1 to 15 and comparative examples 1 to 13, lithium hexafluorophosphate (LiPF) alone was used as the lithium salt6) Lithium difluorophosphate (LiPO)2F2) Lithium tetrafluoroborate (LiBF4), lithium difluorooxalato borate (LiODFB), lithium bis (fluorosulfonyl) imide (LiFSI) due to lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium bistrifluoromethanesulfonylimide (LiN (CF)3SO2)2) Lithium perchlorate (LiClO)4) Tris (trifluoromethanesulfonyl) amide) Methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB) and the like can be used as lithium salts in the reaction for preparing the electrolyte of the present invention, and the lithium salts have the same or similar effects in action and technical effects as those of the substances used as the lithium salts in the examples, and are therefore suitable for the present invention.
The above description is only for the purpose of illustrating the present invention, but not for the purpose of limiting the same, and the present invention is not limited thereto. Numerous simple deductions, modifications or substitutions may be made by those skilled in the art in light of the teachings of the present invention. Such deductions, modifications or alternatives also fall within the scope of the claims of the present invention.

Claims (11)

1. A nonaqueous electrolytic solution comprising a lithium salt, an organic solvent, and an additive comprising an arylsulfate ester and a silicon-containing compound,
the aryl sulfate is aryl sulfate shown in formula A,
Figure FDA0003015711600000011
wherein R is1、R2Each independently is phenyl or polycyclic aromatic hydrocarbon group with 2-3 aromatic rings, or R1、R2Can be connected to form phenyl or polycyclic aromatic hydrocarbon with 2-3 aromatic rings; the phenyl or polycyclic aromatic hydrocarbon group with 2-3 aromatic rings can be substituted by one or more of F, Cl, Br, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, carboxylic ester with 1-10 carbon atoms, carbonyl with 1-10 carbon atoms and cyano with 1-10 carbon atoms;
the silicon-containing compound is a silicon-containing compound shown in a formula B,
Figure FDA0003015711600000012
wherein R is3、R4、R5、R6Each independently F, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a carboxylate group having 1 to 10 carbon atoms, and a phenyl group; the alkyl, alkenyl and alkynyl can be substituted by one or more of O, N, S, F, Cl and Br; the phenyl group may be substituted by one or more of F, Cl, Br, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxylate group having 1 to 10 carbon atoms, a carbonyl group having 1 to 10 carbon atoms, and a cyano group having 1 to 10 carbon atoms.
2. The nonaqueous electrolytic solution of claim 1, wherein the arylsulfate is an arylsulfate represented by the formula A,
Figure FDA0003015711600000021
wherein R is1、R2Each independently is phenyl, biphenyl, naphthyl, phenanthryl; or, R1、R2May be linked to form a phenyl, biphenyl, naphthyl, phenanthryl group; the phenyl, biphenyl, naphthyl and phenanthryl can be substituted by one or more of F, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, methoxy, ethoxy, tert-butoxy, formyl, acetyl, methoxycarbonyl, ethoxycarbonyl, cyano and cyanomethyl.
3. The nonaqueous electrolytic solution of claim 1, wherein the arylsulfate ester represented by the formula A contains one or more compounds selected from the group consisting of,
Figure FDA0003015711600000022
Figure FDA0003015711600000031
4. the nonaqueous electrolytic solution of claim 1, wherein the silicon-containing compound is a silicon-containing compound represented by formula B,
Figure FDA0003015711600000032
wherein R is3、R4、R5、R6Each independently F, methyl, ethyl, isopropyl, t-butyl, methoxy, ethoxy, vinyl, allyl, ethynyl, formate, acetate, formyl, acetyl, cyano, cyanomethyl, or phenyl; the phenyl can be substituted by one or more of F, Cl, Br, methyl, ethyl, isopropyl, tert-butyl, vinyl, allyl, ethynyl, formate, acetate, formyl, acetyl, cyano and cyanomethyl.
5. The nonaqueous electrolytic solution of claim 1, wherein the silicon-containing compound represented by the formula B contains one or more compounds selected from the group consisting of,
Figure FDA0003015711600000041
6. the nonaqueous electrolyte solution of any one of claims 1 to 5, wherein the nonaqueous electrolyte solution contains, by mass, 8.0 to 15.0 parts of a lithium salt, 0.01 to 5.0 parts of an arylsulfuric acid ester represented by formula A, and 0.01 to 5.0 parts of a silicon-containing compound represented by formula B, relative to 70.0 parts of an organic solvent.
7. The nonaqueous electrolytic solution of claim 6, comprising a lithium salt, an organic solvent, and an additive comprising an arylsulfate ester, a silicon-containing compound, and fluoroethylene carbonate,
wherein the organic solvent comprises, relative to 70.0 parts of organic solvent, 8.0-15.0 parts of lithium salt, 0.01-5.0 parts of aryl sulfate shown in formula A, 0.01-5.0 parts of silicon-containing compound shown in formula B and 0.01-15.0 parts of fluoroethylene carbonate.
8. The nonaqueous electrolytic solution of claim 6, comprising a lithium salt, an organic solvent, and an additive comprising an arylsulfate ester, a silicon-containing compound, fluoroethylene carbonate, and other additives,
wherein the organic solvent comprises, relative to 70.0 parts of organic solvent, 8.0-15.0 parts of lithium salt, 0.01-5.0 parts of aryl sulfate shown in formula A, 0.01-5.0 parts of silicon-containing compound shown in formula B, 0.01-15.0 parts of fluoroethylene carbonate and 1.0-5.0 parts of other additives,
the other additive includes one or more of 1, 3-propane sultone, vinylene carbonate, triallyl isocyanurate, 1, 4-butane sultone, 1, 3-propene sultone, methylene methanedisulfonate, ethoxypentafluorocyclotriphosphazene, tris (trimethylsilyl) phosphate, triallyl phosphate, citraconic anhydride, and tris (trimethylsilyl) borate.
9. The nonaqueous electrolytic solution of claim 1, wherein the lithium salt comprises lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium perchlorate (LiClO)4) Lithium bistrifluoromethanesulfonylimide (LiN (CF)3SO2)2) Tris (trifluoromethanesulfonyl) methyllithium (LiC (CF)3SO2)3) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (lidob), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluoro (LiPO)2F2) And lithium difluorobis (oxalato) phosphate (LiDFOP), preferably lithium hexafluorophosphate and lithium difluorophosphate.
10. The nonaqueous electrolytic solution of claim 1, wherein the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, butylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 1, 4-butyrolactone, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl difluoroacetate, difluoroethyl acetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, tetrahydrofuran, and 2-methyltetrahydrofuran, and preferably comprises one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate.
11. A lithium ion battery comprising a nonaqueous electrolyte solution according to any one of claims 1 to 10, a positive electrode sheet, a negative electrode sheet, and a separator.
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